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11.4: Conjugate Pairs and Buffers: When The PH Takes Control
11.4: Conjugate Pairs and Buffers: When The PH Takes Control
We often tend to regard the pH as a quantity that is dependent on other variables such as the concentration and strength of an acid, base
or salt. But in much of chemistry (and especially in biochemistry), we find it more useful to treat pH as the "master" variable that
controls the relative concentrations of the acid- and base-forms of one or more sets of conjugate acid-base systems. In this lesson, we
will explore this approach in some detail, showing its application to the very practical topics of buffer solutions, as well as the use of a
simple graphical approach that will enable you to estimate the pH of a weak monoprotic or polyprotic acid or base without doing any
arithmetic at all!
0.002 mol
Cb = = 0.02M (11.4.2)
0.10 L
0.010 mol
Ct = = 0.10 M . (11.4.3)
0.10 L
Note that this solution would be indistinguishable from one prepared by combining Ca = 0.080 mole of acetic acid with Cb = 0.020
mole of sodium acetate and adjusting the volume to 100 ml.
Thus starting with a solution of a pure weak acid or weak base in water, we can add sufficient strong base or strong acid, respectively,
to adjust the ratio of the conjugate species — that is, the ratios [HA]/[A–] in the case of an acid, or [B]/[BH+] for a base, to any value
we want.
IONIZATION FRACTIONS
To express the relative concentrations of the protonated and deprotonated forms of an acid-base system present in a solution, we could
use the simple ratio [HA]/[A] (or its inverse), but this suffers from the drawback of yielding an indeterminate result when the
concentration in the denominator is zero. For many purposes it is more convenient to use the ionization fractions
− −
[A ] [A ]
α1 = = (11.4.5)
−
[H A] + A ] Ca
The fraction α is also known as the degree of dissociation of the acid. By making appropriate substitutions using the relation
1
[H A]
+
[H ] = Ka (11.4.6)
−
[A ]
Ka
α1 = (11.4.8)
+
Ka + [ H ]
Notice that the the values for both of these functions are close to zero or unity except within the pH range pKa ± 1 (Figure 11.4.1).
As valuable as these plots are for showing how the distribution of conjugate species varies with the pH, they suffer from two
drawbacks:
Plots ofα cover only a single order of magnitude, but the actual concentrations, which we are often more interested in, vary over a
far greater range from pH 0 to 14.
They are of little help if one wishes to estimate the pH of a solution of the acid or base, or of one of its salts.
Both of these limitations are readily overcome by the use of easily-constructed logarithmic plots which we describe in the following
section.
BUFFER SOLUTIONS
The word buffer has several meanings in English, most of them referring (in its verb form) to cushion, shield, protect, or counteract an
adverse effect. In chemistry, it refers specifically to a solution that resists a change in pH when acid or base is added. A buffer (or
buffered) solution is one that resists a change in its pH when H+ or OH– ions are added or removed owing to some other reaction taking
place in the same solution. Buffer solutions are essential components of all living organisms.
Our blood is buffered to maintain a pH of 7.4 that must remain unchanged as metabolically-generated CO2 (carbonic acid) is added
and then removed by our lungs.
Buffers in the oceans, in natural waters such as lakes and streams, and within soils help maintain their environmental stability
against acid rain and increases in atmospheric CO2.
Many industrial processes, such as brewing, require buffer control, as do research studies in biochemistry and physiology that
involve enzymes, are active only within certain pH ranges.
The essential component of a buffer system is a conjugate acid-base pair whose concentration is fairly high in relation to the
concentrations of added H+ or OH– it is expected to buffer against. A simple buffer system might be a 0.2 M solution of sodium
acetate; the conjugate pair here is acetic acid HAc and its conjugate base, the acetate ion Ac–. The idea is that this conjugate pair "pool"
EXERCISE 11.4.1
Sketch out a similar diagram showing what happens when you remove H+ or OH–.
Answer
When this happens, the ratio [HAc]/[Ac–], will remain substantially unchanged, as will the pH, as you will see below.
You can also think of the process depicted above in terms of the LeChâtelier principle: addition of H+ to the solution suppresses the
dissociation of HAc, partially counteracting the effect of the added acid, as illustrated by the equation at the bottom left of the above
diagram.
in which Ct denotes the total concentration of all species in the solution. Because we added a strong (completely dissociated) base
NaOH to the acid, we also note that
+
Cb = [N a ] (11.4.10)
or, since p K
a =– log Ka , we invert the ratio to preserve the positive sign:
−
[A ]
pH = p Ka + log (11.4.14)
[H A]
This equation is known as the Henderson-Hasselbalch Approximation. It tells us that the pH of a solution containing a weak acid-base
system controls the relative concentrations of the acid and base forms of that system.
It is interesting to note that the H-H equation was not developed by chemists!
Lawrence Henderson (1878-1942) was an American medical doctor who taught at Harvard and who studied the acidity of blood
and its relation to respiration. In 1908 he worked out the relation shown in Equation 11.4.11.
In 1916, K. Hasselbalch, a physiologist at U. of Copenhagen, derived the logarithmic form in Equation 11.4.14.
You may wonder why these two equations, whose derivation we now consider almost trivial, should have immortalized the names
of these two scientists. The answer is that the theory of chemical equilibrium was still developing in the early 1900's, and had not
yet made its way into chemistry textbooks. Even the concept of pH was unknown until Sørenson's work appeared in 1909. It was
Of special interest is the case in which the pH of a solution of an acid-base system is set to the value of its pKa. According to the above
equation, when pH = pKa, the log term becomes zero, so that the ratio [AB–] / [HA] = 100 = 1, meaning that [HA] = [AB–]. In other
words, when the pH of a solution is set to the value of the pKa of an acid-base pair, the concentrations of the acid- and base forms will
be identical. This condition can be represented schematically on a proton-free energy diagram:
This says, in effect, that at when the pH of a solution containing both the acid and it conjugate base is made identical to the acid pKa,
the forms HA and A– possess identical free energies, and will therefore be present in equal concentrations.
NOTE
When the pH of a solution is set to the value of the pKa of an acid-base pair, the concentrations of the acid- and base forms will be
identical.
Equation 11.4.12 above and its logarithmic equivalent in Equation 11.4.14 are of limited use in calculations because the exact values
[A–] and [HA] are known only for the special case when the pH of the solution is identical to the pKa. Most buffer solutions will be
adjusted to other pH's, and of course, once the buffered solution begins doing it work by counteracting the effect of additions of H+ or
OH–, both [A–] and [HA] will have changed. These two equations are so widely used in practical chemistry (and especially in
biochemistry) that they are worth committing to memory.
increases [H+] and decreases the pH. So you can always arrange the equation to make it come out right. For these reasons, it is useful
to rewrite the above two equations by replacing the equilibrium concentrations [A–] and [HA] with the known initial values Ca and Cb:
Ca
+
[H ] ≈ Ka (11.4.15)
Cb
Cb
pH ≈ p Ka + log (11.4.16)
Ca
Although these are approximations, they are usually justified because useful buffer systems are always significantly more concentrated
than those responsible for adding or removing hydrogen ions. Also, at these higher ionic concentrations, the Ka of the buffer system
will seldom be precisely known anyway. Don't expect actual buffer pH's to match calculations to better than 5%.
3) The easiest (if not particularly elegant) way to work this out is to initially assume that we will dissolve 1.00 mole of solid NH4Cl
in water, add sufficient OH– to partially neutralize some of this acid according to the reaction equation NH4+ + OH– → NH3 + H2O,
and then add sufficient water to make the volume 1.00 L.
mass of ammonium chloride:
(1 mol) × (53.5 g Mol) = 53.8 g
+
let x = moles of NH4 that must be converted to NH3.
Then Ca/Cb = (1-x)/x = .55; solving this gives x = .64, 1–x = .36.
4) So to make 1 L of the buffer, dissolve .36 × 53.8 g = 19.3 g of solid NH4Cl in a small quantity of water. Add .64 mole of NaOH
(most easily done from a stock solution), and then sufficient water to make 1.00 L.
5) To make 200 mL of the buffer, just multiply each of the above figures by 0.200.
situations in which the simplifying assumptions are not valid. An exact treatment of conjugate acid-base pairs, including a correct
derivation of the Henderson-Hasselbalch equation, is given in the chapter on Exact Calculations.
The approximations that lead to the H-H equation limit its reliable use to values of Ca and Cb that are within an order of magnitude of
each other, and are fairly high. Also, the pKa of the acid should be moderate.
Equation 11.4.19 is simply a re-writing of the equilibrium constant expression, and is therefore always true. Of course, without
knowing the actual equilibrium values of [HA] and [A–], this relation is of little direct use in pH calculations.
Ca
+
[H ] ≈ Ka (11.4.20)
Cb
approximate
Equation 11.4.20 is never true, but will yield good results if the acid is sufficiently weak in relation to its concentration to keep the
[H+] from being too high. Otherwise, the high [H+] will convert a significant fraction of the A– into the acid form HA, so that the ratio
[HA]/[A–] will differ from Ca /Cb in the above two equations. Consumption of H+ by the base will also raise the pH above the
predicted value as we saw in the preceding problem example.
BUFFER INDEX
The terms buffer intensity and buffer capacity are commonly employed as synonyms for buffer index, but in some contexts, buffer
capacity denotes the quantity of strong acid or strong base which alters the buffer's pH by 1 unit. (see below). How effective is a given
buffer system in resisting changes in the pH? The most direct expression of this is the rate of change of the pH as small quantities of
strong acid or base are added to the system: ΔC/Δ(pH). Expressed in calculus notation, this is the buffer index, defined as
∣ dC ∣
β= ∣ ∣ (11.4.21)
∣ d(pH ) ∣
C here refers to the concentration of strong acid or base added to the solution. Because added acid or base affects the pH in opposite
ways, we take the absolute value of this function in order to ensure that β is always positive. The value of β can be calculated
analytically from Ca, Cb, Ka, Kb and [H+]. By taking the second derivative of β, it can be shown that the buffer index has a maximum
value when the pH = pKa.
This alternative view shows how the distribution fractions of HAc and Ac– relate to the effective buffering range of this conjugate pair,
which is conventionally defined as ±1 pH unit of the pKa. The term buffer capacity is an alternative means of expressing the ability of
a buffer system to absorb the addition of strong acid or base without causing the pH to deviate by more than one unit from that of the
pure buffer.
In this example, the buffer capacities for addition of acid and base will differ because the buffer pH has been adjusted to a value that
differs from its pKa.
If you examine this plot carefully, you will see that it is nothing more than a definition of pH and pOH, as well as a definition of a
neutral solution at pH 7. Notice, for example, that when the pH is 4.0, [H+] = 10–4 M and [OH–] = 10–10 M.
Here is a log C plot for a 10–3 M solution of acetic acid ("HAc") in water. Although it may look a bit complicated at first, it is really
very simple. The heavy maroon line on the left plots the concentration of the acid HAc as a function of pH. The blue line on the right
shows how the concentration of the base Ac– depends on pH. The horizontal parts of these lines are aligned with "3" on the –log-C
axis, corresponding to the 10–3 M nominal concentration (Ca).
How do we know the shapes and placement of the plots for the concentrations of acetic acid [HAc] and the acetate ion [Ac–] ?
Although both of these concentrations will of course vary with the pH, their deviations from 10–3 M are too small to reveal themselves
on a logarithmic plot until the pH approaches the pKa.
At very low pH, virtually all of the acetate system will be in its acid form (that is, [HAc] = 10–3), and similarly, at high pH, the base
form [Ac–] = 10–3 M.
When pH = pKa, the concentrations of the conjugate species are identical, as indicated by the crossing of the lines representing the
two concentrations. These concentrations will be half of the total concentration given by Ca, so [HAc] = [Ac–] = ½Ca = 0.5E–3 M.
Where does this go on the log-C axis? Well, the logarithm of 0.5 is –0.3 (a useful fact to remember!), so the crossing point at is
displaced by 0.3 of a log-C unit below the –3 level on the y-axis.
Because point defines both the pKa and concentration of a particular acid-base system, it is known as the system point.
What about the slopes of the plots when they bend down? It turns out that these slopes are +1 for
[Ac–] and –1 for [HAc]. Since the slopes of the lines for [H+] and [OH–] are ±1, we can use these as guidelines; just make the plots
of [Ac–] and [HA] parallel to them.
ESTIMATING THE PH
Of special interest in acid-base chemistry are the pH values of a solution of an acid and of its conjugate base in pure water; as you
know, these correspond to the beginning and equivalence points in the titration of an acid with a strong base. Continuing with the
example of the acetic acid system, we show below another plot that is just like the one above, but with a few more lines and numbers
added.
pH of acetic acid in pure water. Suppose you would like to find the pH of a 0.001 M solution of acetic acid in pure water. From the
equation
+ –
H Ac + H2 O ⇌ H3 O + Ac (11.4.22)
we know that equal numbers of moles of hydronium and acetate ions will be formed, so the concentrations of these species should be
about the same:
+ –
[H ] ≈ [Ac ] (11.4.23)
will hold. The equivalence of these two concentrations corresponds to the point labeled on the logC-pH plot; this occurs at a pH of
about 4, and this is the pH of a 0.001 M solution of acetic acid in pure water.
pH of sodium acetate in pure water. A 0.001 M solution of NaAc in water corresponds to the composition of a solution of acetic acid
that has been titrated to its equivalence point with sodium hydroxide. The acetate ion, being the conjugate base of a weak acid, will
undergo hydrolysis according to
– –
Ac + H2 O ⇌ H Ac + OH (11.4.24)
This condition occurs where the right sloping part of the line representing [HAc] intersects the [OH–] line at in the plot above. As
you would expect for a solution of the conjugate base of a weak acid, this corresponds to an alkaline solution, in this case, at about pH
= 7.8.
You will have to admit that estimating a pH in this way is far more painless than an ordinary numerical calculation would be!
Thus the system point defines the NH4+/NH3 pair (pKa 9.3) at 25°C and a total concentration
CT = Ca + Cb = 0.0010 M . (11.4.26)
To estimate the pH of a solution of ammonia in pure water, we make use of the charge balance requirement (known as the proton
condition)
+ + −
[N H ] + [H ] = [OH ] (11.4.27)
4
which we simplify by assuming that, because NH4+ is a weak acid, [NH4+] >> [H+] and we can drop the [H+] term; thus the
approximation
+ −
[N H ] ≈ [OH ] (11.4.28)
4
which corresponds to the crossing point and a pH of 10.0. Similarly, at the crossing point , [NH3] ≈ [H+]. This comes from the
proton condition
+ –
[N H3 ] + [ H ]– [OH ] = 0 (11.4.29)
OK so far? That's really all we need, but it's usually more convenient to combine these with mass balances on the protons alone, so that
we have a single equation for each of the two solutions. The resulting equations are known as the proton conditions for the two
solutions.
To avoid a lot of algebra, there is a simple short-cut for writing a proton condition equation:
1. Identify the substance you are starting with — the pure acid, base, or salt, and also H2O itself, that make up the solution whose pH
you wish to know at the concentration for which the log C-pH chart is drawn. we call this the proton reference level (if that
appellation scares you, it is sometimes referred to as the "basis substance".)
2. On the left side of the proton condition, write concentration expressions for all species that possess protons in excess of the
reference level.
3. On the right side, write concentrations of all species that possess fewer protons the reference level.
Let's try it for our ammonia system.
Solution of NH3 in water:
The proton reference level (PRL) is defined by NH3(aq) and H2O.
Proton condition: [H3O+] + [NH4+] = [OH–]
(Notice that the substances that define the PRL (in case, H2O and NH3) never appear in the proton condition equation.)
Solution of NH4Cl (or of any other strong-anion ammonium salt) in water:
The PRL is defined by NH4+ and H2O.
Proton condition: [H3O+] = [NH3] + [OH–]
(The chloride ion has nothing to do with protons, so it does not appear here.)
You will recall that we dealt with solutions of the salts sodium acetate and ammonium chloride in the two examples described above.
What is different here is that both components of the salt CH3COONH4 ("NH4Ac") are "weak" in the sense that their conjugate species
NH3 and HAc are also present in significant quantities. This means that we are really dealing with two acid-base systems — the ones
shown previously — on the same plot.
Each system retains its own system point, for the acetate system and for the ammonium system. Note that the two plots previously
shown were for 10–3 M solutions, so the non-system points for this more concentrated solution occur at different pH values. The pH's
of 10–2 M solutions of HAc , NaAc , and NH3 are located by using the same proton conditions as before.
The only new thing here is the point , which corresponds to the ammonium acetate solution in which we are interested. The proton
condition for this solution is [H+] + [HAc] = [NH3(aq)] + [OH–]. Inspection of the plot reveals that [H+] << [HAc] and [OH–] <<
[NH3(aq)], so the proton condition can be simplified to [HAc] ≈ [NH3(aq)], corresponding to the intersection of these two lines at .
POLYPROTIC SYSTEMS
Now that you are able to find your way around log C-pH plots that encompass two acid-base systems, the polyprotic systems that we
describe below should be no trouble at all.
THE CARBONATE SYSTEM
The pH of a 10–3 M solution of CO2, NaHCO3 and Na2CO3 are indicted by the blue annotations.
You should take a few moments to verify the approximations in the rightmost column. Notice the factors of 2 that multiply some of the
concentrations. For example, the "2[CO32–]" term in the first line of the table means that the CO32– species is two steps away from the
proton reference level H2CO3*, so it would take two hydrogen ions to balance a single carbonate ion.
Another new feature introduced here is the doubling of the slopes of the lines representing [H2CO3*] and [CO32–] where they cross the
pH values corresponding to the Kas that are one step removed from their own system points and near –log C = 7.
phosphoric acid (H3PO4) [H+] = [H2PO4–] + 2[HPO42–] + 3[PO43–] + [OH–] [H+] ≈ [H2PO4–]
[H+] + [H3PO4] ≈
sodium dihydrogen phosphate (NaH2PO4) [H+] + [H3PO4] = [HPO42–] + 2[PO43–] + [OH–]
[HPO42–]
disodium hydrogen phosphate (Na2HPO4) [H+] + 2[H2PO4–] + [H2PO4–] = 3[PO43–] + [OH–] [H3PO4-] = [PO43–] + [OH–]
+
trisodium phosphate (Na3PO4) [H ] + 3[H3PO4] +2 [H2PO4–] + [HPO42–] –
= [OH ] [HPO42–] ≈ [OH–]
Because the phosphate plot is rather crowded, we show here a modified one in which the details of the pH estimates for the solutions of
H3PO4 and its salts are emphasized.
Estimation of the pH of 10–3 M solutions of phosphoric acid and trisodium phosphate , based on the approximations in the above
table are straightforward.
Those for NaH2PO4 and Na2HPO4 , however, are complicated by the presence of two concentration terms on the right side of the
respective proton condition approximations.
Unless you are in an advanced course, you may wish to skip the following details. The important thing to know is that graphical
estimates of these more problematic systems are fundamentally possible.
Thus for sodium dihydrogen phosphate, if we were to follow the pattern of the other systems, the approximation at the crossing point
would be
[H+] = [HPO42–], corresponding to point . But inspection of the plot shows that at that pH (4.0), the concentration of H3PO4 is ten
times greater than that of H+ (point ). A rough estimate of the pH can be made by constructing a line (shown in red) that is parallel to
those for H3PO4 and H+, but is raised up by a factor of 10. This results in the new crossing point .
Similarly, the pH of a disodium hydrogen phosphate solution does not correspond to the crossing point because of the significant
value of [HPO43–] at this pH. Again, we construct a line above this crossing point that predicts a pH corresponding to point .
Although these stratagems may seem rather crude, it should be noted that the uncertainties associated with them tend to be minimized
on a logarithmic plot. In addition, it should be borne in mind that in a solution as concentrated as 0.1M, the pKa values found in tables
are not applicable. The alternative of solving for the pH algebraically, taking into consideration activity coefficients for the high ionic
concentrations, is rarely worth the effort.
For any given acid-base system, you need to know the pKa and nominal concentration CT.
Find the point at which these two lines intersect.
Locate and mark the system point on the pKa line. It will be 0.3 of a log-C unit below the concentration line.
This is where [HA]
= [A–] = ½ Ct . (Recall that log.5 = .3)
For pH < pKa, [HA] plots as a line through the system point with slope = 0.
For pH > pKa, the line assumes a slope of –1. Use the [H+] and
[OH–] lines as guides.
In the pH interval of ±pKa, the slope changes from 0 to +1. You can approximate this with a sloped line as shown, or
"prettify" it with a smooth curve.
Finally, draw the lines for the conjugate form [A–], using slopes +1 and 0.
REFERENCES
1. Boundless outlines on buffer solutions. These summarize the main points and problem examples as presented in major textbooks.
They are an excellent aid for pre-exam review. Chemistry: The Central Science (8 subtopics)
2. A collection of practice exercises (with solutions) on buffers and titrations from Bryn Mawr College.
3. The Henderson-Hasselbalch equation: its history and limitations - Henry N. Po and N.M. Senoza, J.Chem. Ed. 78 (11) 2001 (1499-
1503)
4. A detailed treatment of log-C vs pH diagrams can be found in the book Acid-base diagrams by Kahlert and Schotz. It is available
online in some college libraries.
CONTRIBUTORS
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook